Challenges in assignment of orbital populations in a high spin manganese(<scp>iii</scp>) complex

Fitzpatrick, Andrew; Stepanović, Srdjan; Müller‐Bunz, Helge; Gruden, Maja; García‐Fernández, Pablo; Morgan, Grace G.

doi:10.1039/c5dt03914b

Cited by 13 publications

(9 citation statements)

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“…The HOMO and LUMO orbitals of the two Mn(III) complexes were found to be very similar. Computational studies suggested that the geometry of the ligand does not prevent the possibility of SCO, contrary to what was found for the Morgan systems [73,74]. 5 Complexes, HS (S = 5/2) and LS (S = 1/2)-Fe(III)…”

Section: Results Solid Statecontrasting

confidence: 65%

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

2020

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The capability of a given substance to change its spin state by the action of a stimulus, such as a change in temperature, is by itself a very challenging property. Its interest is increased by the potential applications and the need to find sustainable functional materials. 3D transition metal complexes, mainly with octahedral geometry, display this property when coordinated to particular sets of ligands. The prediction of this behavior has been attempted by many authors. It is, however, made very difficult because spin crossover (SCO), as it is called, occurs most often in the solid state, where besides complexes, counter ions, and solvents are also present in many cases. Intermolecular interactions definitely play a major role in SCO. In this review, we decided to analyze SCO in mono- and binuclear transition metal complexes containing halogens as ligands or as substituents of the ligands. The aim was to try and find trends in the properties which might be correlated to halogen substitution patterns. Besides a revision of the properties, we analyzed structures and other information. We also tried to build a simple model to run Density Functional Theory (DFT) calculations and calculate several parameters hoping to find correlations between calculated indices and SCO data. Although there are many experimental studies and single-crystal X-ray diffraction structures, there are only few examples with the F, Cl, Br and series. When their intermolecular interactions were not very different, T1/2 (temperature with 50% high spin and 50% low spin states) usually increased with the calculated ligand field parameter (Δoct) within a given family. A way to predict SCO remains elusive.

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Section: Results Solid Statecontrasting

confidence: 65%

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

2020

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“…They are close to the values observed in the [Mn(3,5-diBr-sal-N-1,5,8,12)] + BPh 4 À complex at 250 K. [19] The bond angles XÀ Mn-X deviate from ideal 90/180 °values showing significant distortion of the Mn III N 4 O 2 octahedron typical for the HS state. The octahedral distortion parameters (Σ, Θ and ζ) calculated using the OctaDist [4,23] tool are listed in Table 1.…”

Section: Crystal Structuresmentioning

confidence: 99%

“…Octahedral distortion parameters were calculated within OctaDist software. [23] The powder XRD patterns for 1-3 were recorded at room temperature on an Aeris diffractometer (Malvern PANalytical B.V., Netherlands). The powder XRD measurements showed that all polycrystalline samples 1-3 are monophase crystalline materials corresponding to the single crystal data (Figure S1).…”

Section: X-ray Crystallographymentioning

confidence: 99%

Abrupt Spin‐State Switching in Mn(III) Complexes with BPh₄ Anion: Effect of Halide Substituents on Crystal Structure and Magnetic Properties.

Tiunova

Kazakova

Корчагин

et al. 2021

Chemistry A European J

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Three tetraphenylborates of mononuclear Mn(III) cation complexes with hexadentate ligands, the products of the reaction between a N,N'-bis(3-aminopropyl) ethylenediamine and salicylaldehydes with the different haloid substitutions at the 5 or 3,5 positions, have been synthesized: [Mn(5-F-sal-N-1,5,8,12)]BPh 4 (1), [Mn(3,5-diCl-sal-N-1,5,8,12)]BPh 4 (2) and [Mn(3,5-Br,Cl-sal-N-1,5,8,12)]BPh 4 (3). Their crystal structure, dielectric constant (ɛ) and magnetic properties have been studied. Ligand substituents have a dramatic effect on the structure and magnetic properties of the complexes. With decreasing temperature, the complex (1) shows a gradual spin crossover from the high-spin state (HS) to the HS:LS intermediate phase, followed by an abrupt transition to the low-spin state (LS) without changing the crystal symmetry. The complexes 2 and 3 are isostructural, but have fundamentally different properties. Complex 2 demonstrates two structural phase transitions related to

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“…In recent years, noncovalent interactions, such asstacking and hydrogen bonding, have been shown to be a new channel for magnetic exchange in supramolecular chemistry (Fukuroi et al, 2014;Hicks et al, 2001;Atzori et al, 2014;Fitzpatrick et al, 2016). [Fe(HL) 2 Cl 4 ] (L is 2-aminopyrazine) is a discrete complex having a 2D layer structure formed by halogen bonding between Cl and the N atom of the amine substituent on the pyrazine moiety of an adjacent complex.…”

Section: Propagation Of Magnetic Interactions Through Hydrogen Bondingmentioning

confidence: 99%

A survey of interactions in crystal structures of pyrazine-based compounds

Taghipour

Mirzaei

2019

Acta Crystallogr C

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The important role of pyrazine (pz) and its derivatives in fields such as biochemistry and pharmacology, as well as in the study of magnetic properties, is surveyed. Recognition of these properties without extensive investigations into their structural properties is not possible. This review summarizes interactions that exist between these organic compounds by themselves in the solid state, as well as those in coordination polymers with metal ions and in polyoxometalatebased hybrids. Complexes based on pyrazine ligands can generate metal-organic framework (MOF) structures that bind polyoxometalates (POMs) through covalent and noncovalent interactions. Some biological and magnetic properties involving these compounds are considered and the effect of hydrogen bonding on their supramolecular architectures is highlighted. feature articles 232 Taghipour and Mirzaei A survey of interactions of pyrazine-based compounds Acta Cryst. (2019). C75, 231-247 feature articles 234 Taghipour and Mirzaei A survey of interactions of pyrazine-based compounds Acta Cryst. (2019). C75, 231-247 feature articles Acta Cryst. (2019). C75, 231-247 Taghipour and Mirzaei A survey of interactions of pyrazine-based compounds 237 Figure 9Structure of [Cu 2 (PZOAPZ-H)Br 3 (H 2 O) 2 ]. Reproduced from Grove et al. (2004) with permission. feature articles Acta Cryst. (2019). C75, 231-247 Taghipour and Mirzaei A survey of interactions of pyrazine-based compounds 245

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Challenges in assignment of orbital populations in a high spin manganese(iii) complex

Cited by 13 publications

References 53 publications

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

Abrupt Spin‐State Switching in Mn(III) Complexes with BPh₄ Anion: Effect of Halide Substituents on Crystal Structure and Magnetic Properties.

A survey of interactions in crystal structures of pyrazine-based compounds

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Challenges in assignment of orbital populations in a high spin manganese(iii) complex

Cited by 13 publications

References 53 publications

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

Abrupt Spin‐State Switching in Mn(III) Complexes with BPh4 Anion: Effect of Halide Substituents on Crystal Structure and Magnetic Properties.

A survey of interactions in crystal structures of pyrazine-based compounds

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Abrupt Spin‐State Switching in Mn(III) Complexes with BPh₄ Anion: Effect of Halide Substituents on Crystal Structure and Magnetic Properties.